Catalysis Science & Technology
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Prabhakar, C. S. Reddy, M. N. Eberlin, and L. S. Santos Chem. Eur.
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room temperature. The solution was cooled to 0 °C using an ice bath.
Then NaNO2 (278 mg, 4.04 mmol) in 2 mL water was added in small
portions. After stirring at 0 °C for 20ꢀ30 min, an aqueous solution of
NaN3 (263 mg, 4.04 mmol) was slowly added and the mixture was stirred
for additional 2 h at room temperature. After completion, the reaction
mixture was extracted with diethyl ether (3 x 40 mL). The combined
organic fractions were washed with saturated NaHCO3 solution (2 x 40
mL) and brine (2 x 40 mL). The organic fractions were dried over Na2SO4
7
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and evaporated under reduced pressure to provide the azide 1g (513 mg,
1
10 90%) as a brown oil. H NMR (400 MHz, CDCl3): 7.46 (d, J = 10.6 Hz,
1H), 6.88 (d, J = 3.0 Hz, 1H), 6.72 (dd, J = 10.6, 3.6 Hz, 1H), 2.38 (s,
3H); 13C NMR (100 MHz, CDCl3): 139.5, 139.1, 133.3, 121.1, 120.2,
117.9, 22.9; IR: 3306.0, 3224.1, 2954.7, 2504.0, 2425.3, 2324.3, 2241.2,
2110.0, 2065.3, 1602.2, 1474.2, 1380.2, 1304.7, 1202.3, 1149.4; HRMS
15 (ESI) calcd for C7H7BrN3 [M+H]+: 211.9823; Found: 211.9785.
General procedure for the reduction of azides using Fe3O4: To a
solution of azide 1 (1 mmol, 1 equiv) in water (4.0 mL), Fe3O4 (116 mg,
0.5 mmol) and hydrazine monohydrate (0.243 mL, 5 mmol) were added
to the mixture. The reaction mixture was refluxed or heated in a sealed
20 tube at 120 °C under an argon atmosphere until completion, as monitored
by TLC. The reaction was cooled and the Fe3O4ꢀMNPs were separated
using a magnet. The aqueous layer was extracted with ethyl acetate (3 x
10 mL). The combined organic extracts were washed with water and
brine, dried over Na2SO4 and evaporated under reduced pressure. The
25 crude product was purified by flash chromatography (EtOAc/hexanes
eluent) to afford the desired pure amine. (Most of the amines were
analytically pure before flash chromatography). The recovered catalyst
was washed with methanol (2 x 5 mL), dried under vacuum, and reused
for the next cycle of the reaction.
8
9
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